Photographic material and process for the production of multicolor pictures



Dec. 12, 1939. l B. GASPAR I 2,183,394

PHOTOGRAPHIQ MATERIAL AND PROCESS FOR THE PRODUCTION 0F MULTICOLOR PICTURES Filed 'July 27, i957 Fgg.

www www we XXXXX ATT NEYS.

mandante '12, 1939 u1u-Tuofsf-rarasv PATENT: oel-"ics, A

amsn

rno'rooa'srmo mmm.

buenos or mrrooma vIOR. m PIUI'URES.

'AND ruocussA 'V I Beh Gaspar, Brussels-Forest, Belgium application sul; zu, 193i. sei-m In Germany March 24,

tinua'tion-in-partvof my prior applications Ser.

No. 662,396 med'hlal'. 23, 1933/and Ser. No. 1,437 filed Jan. 11,1935. 1

The use' of coloredA light sensitive layers in a multi-layer photographicmaterial has many adf vantages over the use of a coiorless'multi-layer,

material, the layers of which have to be selectively dy'ed after in order to obtain a multicolor image. the ease with which eachof the iight sensitive emulsions maybe uniformly predyed before it is coated on the support, as compared to the dimc'ulty of selectively dyeing vthe various colorless lemulsions layers on the Support after they have ybeen exposed v 4 Itwill be Aunderstood 'that if all of the layers of the exposure material are colored, part o! the visible light is absorbed at the surface of the front layer andy .thereforeeannot produce a silver image'in the layer. It is, Afor this reason, out of the question to record all of the visible light spectrum from one side of a multi-layer exposure material in which all of thejlayelsY are predyed and the absorption characteristics of said dyestuffs overlap to produce lmore or less complete absorption throughout the visible spectrum. In

A practice, itis possible to conline the absorption' resulting from the coloration of "the A.front layer to 'a narrow range of the spectrum so as not Ato substantially impair thecorrect reproduction olf a natural color. 0n the other handit is desirable to avoid this absorption during exposure and to allow. all ofthe visible light to be utilized in the formation ofthe image.-

In my Patent lNo..1,985,3114, December 25, 1934,

o I` have exposure'material-for the production of multicolor images in which all of the layers are uniformly dyed -with dyestufls used later on-in the process for the formation of the color image. the layers being inseparably superimposed to form a multi-layer photographic material. In my prior patent, the dyestuis used in the various layers are so selected that a pervious gap remains, us allowing light to penetrate the sensitized layer and to produce a silver image. therein. By this arrangement al1 ofI the layers oi the material may be exposed from one side.

According to the present invention, .the necessity of dyeing the layers with dyes having gaps The principal advantage is No. 1564031 im (ci. vs -z) Y in their absorption characteristics is avoided by employing an exposure material, in whlch'part of the light sensitive layers are colorless so that all of the exposure light can be recorded from one side. t

`As pointed out above, the colorless front layer or layers may contain dyestui forming substances 'which can subsequently be converted into vdyestus or these layers may be subsequently colored by anywell known coloring process. In such a material it is possible to expose all ofthe layers of the multi-layer exposure material, so as to obtain color separation images of the original subject in silver. Since part of these layers are already predyed and the colorless layer or layers may vcontain dyestufl forming substances or may be subsequently dyed, multicolor master images may thereafter be obtained by selectively 'removing or forming the dyestui yunder the inuence of the color separation images composed of silver. In converting the silver imagesinto 'color images, I may proceed, for example, as set` forth in my prior Patents 1,956,017, April 24, 1934; 2,020,775, November 12, 1935; and 2,004,625, June 1l, 1935. A

It is therefore an object of my invention to provide a multi-layer photographic material having both-colorless and colored sensitized layers, which material is adapted to record all of the visible exposure light from o ne side.

In the practice of my invention I do not need to use dyes for the colored layers which mecum-1v ,plementary to the sensitivities of. said layers,

nor do I need to use dyes which are the same as the sensitivities of these layers. This departure from previous lines of endeavor leads to the production of a.' multicolor vimage which does not ,reproduce the original subject in its, natural colors. vSuch an image may be usedas a master image from' which multicolor copies can be made, reproducing the subject in its natural colors. A copying material suitable for use in this connection is described and claimed inmy copending application Serial No. 642,960, filed November 16, 1932. The color sensitization of the single-layers 4Ain the copying material iscomplementary -to the The exposure material of the present invention is preferably in the form f a multi-pack Itis therefore possible to separate at least one of the layers from the others so that it may later be used independently for copying aiaasoe "LI purposes. For example, it isipossible to expose.

one of the inseparably .superimposed and predyed layers of a copying material from the back while the other layers of the copying 'material are exposed from Athe front. By this arrange- .ment, I have permitted a much greater liberty with respect to the sensitisationof theinseparably superimposed layers of the copying material. Also I have provided a flexible arrangement of terial and in the copying material. For example, the single layer of the exposure material which is adapted to be separated from the others may be dyed blue-green, sensitized to record -the -blue `process to expose a red sensitized yellow dyed layer. On the other hand the same single layer of the exposure material may be dyed magenta. sensitized'to record -the same blue part picture. and may be used to expose a green-sensitive yellow dyed layer of the copying material. The choice of these two alternatives depends upon the color ofthe layer abov'e the yellow dyed layer in the copying material. For example, if the upper layer contains a green vabsorbing dyestui! transmitting red, thesingie layer of the exposure material will be dyed blue-green, as set forth iirst above.

It is therefore a further object of my invention to provide an improved exposure materialhaving colored layers, in which the colorl oi.' the predyed layers is independent of the color of the separation image which it is desired to record in said layer.

In accordance with-the present invention, I have also found thatsince I/am not limited in the selection of the dyestuii's in the colored layers. I may soselect them as to do away with the vnecessity for filter dyestuils in certain layers during exposure, which dyestuils have later to b washed out. To do this I impart to these dyestuifs a dual function, namely. the function of acting as a filter iforV the layer in which they are incorporated, as well as for the layer situated as thereunder, and also the function oi' remaining' in the layer to produce a dyestuff image corresponding to the silver image. Thus the dyestuif present in an overlying layer screens theunderlying layer against light rays to which it may be sensitive, but which it is not desiredto record therein, and the underlying layer is therefore ei'- fectively insensitive to these rays.

Accordingly, it is a fin'therobject of my invention to provide a multi-layerphotographic material having colored layers in which the dxstufis in the colored layers actboth as a filter and as an image-forming material. In the accompanying drawing, Figure 1 illustrates diagrammatically the relative absorption characteristics and sensitivities of the layers in the preferred embodiment of my invention. Hg-

ure 2 represents a similar diagrammatical illustration of a different arrangement of absorption characteristics and relative sensitivities. Figure 3 represents a similar diagrammatical illustration of still another embodiment of my invention. Figure i represents va'diagrammatical illustration of the relative absorption characteristics and sensitivities of the layers in a typical copying material 'I0- Figure 5 and Figure 6 referto diagrammatical illustrationsV noi the relative absorption characteristics and sensitivities of the layers in a modiflcation of my invention, wherein the light sengg sitive layers are in a more close contact.

. .transparent support A carries onthe front therecolors and sensitivities both in the 4exposure mapart picture, and may be used in thef copying for use in conjunctionwith my exposure material.

"Referringtol'lgurehwhiehisexsmplsryofa @H911 mlh-s-.multi-wk photosranhic msterialin which diifes'ent layers L 'II and vmarecombinedwithtwomppottsaandlktbe of 'a colorless blue-sensitive, i. e., not specially sensitized,larer1. Ontherearoi'thenipport A is a yellow low-dyed green sensitive layer II. On the front of support B is a red-dyed redsensitive layer III.` The supports A and B may l. consist, for example. of Celluloid or acetyl 'cellu- On the cross-section illustrated in Figure 1, I'have projected a spectrum which commences at the left of the ngure with the infra-red rays u and extends over the entire visible spectrum. The vertical lines which cutall o! the layers show. as indicated by the legends, the wave lengths. For example, the legend 800m. indicates approximately the line of separation between the n red and green spectral sones, and the legmd 500 indicates approximately the separating line between the green and blue spectral sones. The obliquely shaded areas indicate the absorption curves of the dye used to color the layer.f vThe l vertically shaded sones indicate that vthe exposurelig'htwhichpenetratestbematerialfromthe .surface oftheiaver Llsscreenedbythesbsorption of'an overlying layer. The :r's in the figure mmcscheranreofzhemmmwiihrnpmlf to which the particular layer is sensitive. Thus. for example, it is'seen in llgnre i, the coloris. ,front layer I is sensitive for the blue spectral sone. ALayer 1I is sensitive ier-the green spectral' zone and colored by a yellow. dye whose absorption characteristic fal'in tbe blue spectral sono. This dye may be, for example. phenine G, 304 Schultz dyestuii tablesan the'lsnr my be sensitized with respect to with bens-thio-pseudocyanin ing the blue rays .transmitted irontlayerlandalsoserves ess forthe formation of a III is sensitized inthelred example. for pinacyanolasd dye whosel absorption characteristic falls in the green and blue spectral sones.' be, for example. Diamine Fast Pink number) or anthosine BN (referred 1926). Thus. layer III is light absorbing in the blue spectral sone. and. in` addition to thi, it is screened from the 'expoaire light in the blue spectral soneby reason of theblue absorption IIa and ma, with respect to the supports A and B, is the same as in Figure 1. Layer Ia is colorless and has the same sensitivity as layer I in Figure 1. Layer IIa likewise has the same sensitivity and color absorption characteristic as layer II in Figure 1. Thedyestui! and sensitiser used in this layer may be the same as that used ln layer II of Figure 1. In layer ma, a yellow dye is used having the same absorptionI characteristic as Vthe yellow dye used in layer IIa. This may be a'yellow dyestui! such as chrysophenine G. esame as the dyestui! used in layer IIa. Thus lerlim'ha's anabsorption characteristic in the u blue spectralrange as well as in the blue spectral range by the yellowv dycstui! in the overlying layer 11a. Layer IIIa is sensitized for the red spectral zone', the same as layer. III in -Figure 1, and is. effectively insensitive to bluedue to the blue absorption ofthe overlying yellgsw layer' II, as well as yellow'dye in the layer i elf.

Figure 3 shows a relative arrangement of dye- .stuils and sensitivities .practically the 'same as in Figure 1. The only diiIerence in'this respect is that in IIIb, I have illustrated a dyestuii' having an absorption characteristic in the green spectral zone, for example, a magenta dyestui'i. This layer IlIb difiere from layer III in that the 'absorption characteristic of the dyestu does not extend through the green and blue spectral Y zones, and this layer, instead of being light-absorbing. in the blue spectral z'one, is merely f screened by the blue absorption of the yellow dyestui in theoverlying layer IIb. A suitable dyestui for layer IIIb is Diamine Fast Pink G or SiriusRuby. The mainv difference between Figure 3 and Figure 1 is that the colorless layer Ib is carried on the `back 'of the support A; the yellow-dyed layer IIb is carried on the iront of the back support, and the purple red-dyed layer IIIb is carried on the rear of the back support B. Thus,. the front illm comprising the transparent l support A and layer Ib, is-an ordinary nlm with ent No. 1,956,017, April 24, 1934, or any other desired dyestuillforming substance.

It is also possible to color the front colorless ple Diamine Pure Blue FF. The layer V has inp layer by toning or any other well known process. For example, it may be subsequently colored with a blue dyestuii, for example, Diamine Pure Blue a FF, 424 (Schultz dyestuii tables).

It is particularly important that the amounts of the dyestuii's, or the dyestuiT-forming substances incorporated inthe layers, be exactlydetermined beforehand in order that one may always obtain in the photographic material an imagewhich is colored to exactly the same degree;

of a typical copying material. This material is a multi-layer material having a support with one layer IV on one side of the-support and two layers V and-VI on the other side of .the support. As indicated in the iigure,-the layer IV has incorporated therein a blue-'green dyestuil, for examcorporated therein a yellow 'dyestuiL for example, chrys'ophenine G, and the layer VI` has incorporated therein y'a magenta dyestuil, for example, .Sirius Ruby. Layer IV is sensitized in the green y. spectral region with erythrosine, layer -V inthe red spectral region with pinacyanol,

and layer VI' in the blue spectral region.

In copying from a master image produced in the material of Figurel, onto the copying -material illustrated in Figure 4, the iront film in Figure 1 is first separated from the back film and the image in' layer III is transformed into a red dyestui image in accordance with the dye In Figure 4, I have illustrated a cross-section 3*' des process described in my prior- Patent 2,020,775,.November 12, 1935. It is then possible to print the red dyestuii image thus produced in layer III, which is carried by support B, into layer rv of the material shown. in nuire .Si

4. 'rms is done by printing from the blue-green. 'side of Figure 4, and using a green printing light. .Since layer IV is green-sensitive, and

since the red image in layer'III acts in a shading fashion, one may reproduce in layer IV a silver It' image corresponding to the red image in layer I lI. This silver image may' later be converted to .a blue-green Ac lyestui! image gin accordance with the dye destruction processesreferred to above. The image originallyproduced in `layer lll` III oi' Figure 1 was a red color-selection picture Aand we riow have a correspondingpart-picture 'dyestum such as Diamine Pure Blue FF and after having produced by dye-destruction in layer I of Figure 1 a blue colored image corresponding tothe bluecolor-selection picture therein.

and a yellow picture in layer'lI oi Figure 1 the front film with its yellow image in layer vII and its blue image in layer I is printed into layers .VIand V from` the magenta colored side of the material illustrated in Figure 4. Utilizing' .a A white printing 1ight,the yellow image inlayer- II will iniluence'the blue portion oi t e 'printing light which acts on the blue-sensitive layer VI, thus producinga corresponding silver image in this layer. Similarly, the blue image. in layer4 I will iniluericel the red portion ofthe printing 35 light which acts -on the red-sensitive layer V, thus producing a correspondingsilver image in layer V. 'Ihe portion of the printing light taliing in the green spectral zone will have no eiect,

since it is absorbed at the surface ot layer VI a).

by, the magenta dye incorporated therein. By utilizing the .color destruction processes, above referred to,.a magenta colored image may be produced in layer-VI corresponding tothe yellow image in-layer II.' In like manner, a yellow 45 .image will be produced in layer V corresponding to the blue image in layer I. .Since layer Il is 'green-sensitive. it contains the green color-selection picture which is represented therein by a yellow color 'and which is reproduced in layer 5u'. VI in a magenta color. The image recorded in layer VI is therefore seen 4to be colored complementary to the. color-selection picture recorded in layer II. Similarly, the yellow colored -part image in layer V is complementary to the blue' 55. color-selection recorded in'layer I.

The master image produced in the material o! Figure 2 may be copiedintol the printing material, illustrated in Figure 4, in the same way that 'a master image, according to Figure l, is copied, 00.

except that this time the layer IV of Figure 4 must be made blue-sensitive instead of greensensitive, in order that the yellow image in layer IIIa wiil'act in a shadingv fashion when -printed .into :Figure 4 from the top. In such a case, the 65 fact that both layers IV and VI of Figure 4 are blue-sensitive, will cause no diiilculty since layers IV and VI are printed from opposite sides of the material and the intervening layer V contains 4a yellow dye which has an absorption character- 70- istic in the bluespectral range and therefore acts as a blocking layerbetween layers IV and VI; lIn printing a master image produced in the material of Figure 8, the process'is carried out in'the same way except that layers Ib and IIb 15 sensitive to the other primary colors, a second silver halide layerpredominantly sensitized -for one of the other primary colors` and colored yellow byv a dyestuff which is not removable by ordinary photographic treating baths but which is selectively removable under the inuence oi the photographic image and which transmits light .for

which the third layer is sensitive, and a third-` silver halide layer predominantly sensitized form the remaining primary color and colored by a dyestuff which is not removable by ordinary photographic treating baths but which is selectively removable under the influence of theA photographic image and which absorbs light rays for which the yellow layer is sensitized, the light transmission characteristic of saidmaterial being such that -all of said layers can be exposed from the front of said material to light for which they are predominantly sensitive. y

3; A material for color'photography comprising at least three superposed silver halide emulsion layers each of which is sensitive to oneof three primary colors including a colorless silver halide front layer containing a colorless dyestui forming substance and being predominantly sensitized to the blue spectral region and substantiallyv insensitive tothe other primary colors, a second silver halide layer predominantly sensitized for one of the other primary colors and colored yellow by dyestui which is not removable by ordinary photographic treating baths but which is selectively removable under the iniiuence of the photographic image and which transmits light for which the third layer is senincluding a colorless layer vpredominantly sensitized for the blue `spectral region coated on the front support and substantially insensitive to the other primary colors, a second layer predominantly sensitized for one of the other primary colors and colored yellow by a dyestui which is not removable by ordinary photographic treating baths 4but which is selectively removable under the influence of the photographic image and' which transmits light for which the third layer is sensitive, said second layer being coated on one of the two supports and located between the colorless layer and the third layei' which is predominantly sensitive to the remaining primary color but effectively insensitive tolight for which the second layer is predominantly sensitized and which is transmitted therethrough, said third layer being coated on the rear support, the light transmission characteristic'of said material being such that all of said layers can be exposed from the front of said materialto light for which they are predominantly sensitive.

5;.A multi-pack material for color photography comprising two transparent supports and at least three silver halide emulsion layers, each of which yis sensitive to one of three primary colors including a -colorless layerA predominantly sensitized for the blue spectral region coated on the front support and substantially insensitive to the other primarycolors, a second layer predominantly 'sensitized for vone of the other primary colors and colored yellow by a dyestui which is not removable by ordinary photographic treating baths but which is selectively removable under the influence of the photographic image and which transmits light for which the third layer is sensitive, said second layer .being coated on one of the two supports and located between the colorless layer and the third `layer which ispredominantly sensitive to the remaining primary color, said third layer being colored by a dyestui which is not removable by ordinary photographic treating baths but which is selectively removable under the influence of the photographic image and which absorbs light rays for which the yellow layer is sensitive, said third layer being coated on the rear support, the light` transmission characteristic of said material being such that all of said layers can be exposed from thei'ront of said material to light for which they are predominantly sensitive.

6. A material for color photography comprising at least three superpoaed silver halide emulsion layers including a colorless silver halide front layer predominantly sensitized for the blue spectral lregion and substantially insensitive to the other primary colors, a second `silver halide layer predominantlysensitized for green and colored yellow by a dyestui which is not removable by ordinary photographic treating baths but which is selectively removable under the influence of the photographic image and which transmits light for which the third layer is-sensitive, and

a third silver halide layer predominantly lsensitized for red but effectively insensitive to light for. which the second layer is predominantly sen-A sitive and which is transmitted therethrough,

the light transmission characteristic of said material being such that all of said layers can be exposed from the front of said material to light for which they are predominantly sensitive.

` 7. A material for color photographycomprising' at least three superp'osedv silver halide emulsion layers including a colorless silver halide front layer predominantly sensitized for the blue lspectral region and substantially insensitive to theother primary colors, a second silver halide layer predominantly sensitized for green and colored yellow by' a dyestuif which is not removable by ordinary photographic treating baths but which is selectively removable -under the in- -fluence of the photographic image and which transmits light for which the third layer is sensitive, and a third silver halide layer predominantly sensitized for'red and colored red by a dyestuii' which is not removable by ordinary photographic treating baths but whichl is selectively removable under the iniiuence of the photographic image.

8. A multi-pack material for color photography comprisinga colorless predominantly blue sensitive silver halide emulsion layer on the front -of the first support, said'layer being substantially insensitive to the other primary colors, a predominantly green sensitive silver halideemulsion4 colored yellow by a dyestuil which is not removable by ordinary photographic treating baths but which is selectively removable under the iniluence of the photographic image and which transmits light for which the third layer is sensitive coated on the rear of the nrst support, and a predominantly red sensitive silver/halide emulsion colored red by a dyestui! which isnot removable. by`` ordinary photographic treating baths but which is selectively removable under the influence or the photographic image coated on the iront oi' the second support.

9. A multi-pack material for color photography comprising a colorless predominantly blue sensitive silver halide emulsion layer containing a colorless dye-forming material on the front of the iirst support said layer being substantially insensitive to the other primary colors, a predominantly green sensitive silver halide emulcolored yellow by a dvestui! which is not removable byl ordinary photographic treating,

baths but which is selectively removable under the iniiuence o! the photngraphic image and v.which transmits light .for which the third layer is sensitive coated on the rear of the nrst support,

the other primary colors, a second silver halide layer predominantly sensitized for green and colored yellow by a dyestui! which is not removable 'by ordinary 'photographic treating baths but which is selectively removable under the iniluence of the photographic image and which transmits light for which the third layer is sensitive,

v and a third silver halide layer predominantly sensitized for red and colored yellow by a dyestui! which is not removable by ordinary` photographic treating baths but which is selectively removable under the inuence oi' the photo- `graphic image.

1l. A multi-pack material for color photography comprising a plurality of diiierently sensiti'sed silver halide emulsion layers supported iace to face between a. pair oi' supports, one of said layers beingl a colorless blue sensitive layer which is substantially insensitive to the other primary colors, said one layer being supported on the support through which exposure light initially passes, the second one of said layers being predominantly sensitized for one of the other primary colors and colored yellow by a dyestuif which is not removable by ordinary photographic treating baths but which is selectively removable under the inuence oi a silver image, the third one oi' said layers being predominantly sensitive to the remaining primary color but effectively insensitive to light for which the second layer is predominantly sensitized and which is transmitted therethrough, the light transmission'characteristic oi' said material being such that all ol layers can be exposedfrom the iront ofsaid material to light for which they are predominantly sensitive;

I2. A multi-pack material for color photography comprising a plurality oi diii'erently sensitised silver halide emulsion layers supported iface te` face between a pair or supports, one of said layers being a colorless blue sensitive layer having a dyestui! forming substance incorporated therein and being substantially insensitive to the other primary colors. said 'one layer being supported on the support through which `exposure light initially passes. the second one of said layers being predominantly sensitiseil for one of the other primary colors and colored yellow by a dyestu!! which is not removable by ordinary photographic treating baths buty which is selectively removable under the influence of a silver image,

the thirdone of said layers being predominantly insensitive to the other' primary colors, a predominantly green sensitive silver halide emulsion colored yellow by a -dyestu which is not removable by ordinary photographic'treating baths but which is selectively removable under the innuence of the photographic image and which transmits light for which the third layer is sensitive coated on the rear oi' the iirst support. andv a predominantly red sensitive silver halide emulsion coated on the front of the second support, the light transmission characteristic of said material being such 'that all oi' said layers can be exposed trom the front of said material to light for which they are predominantly sensitive.

14. A material -for color photography comprising at least three superposed silver halide emulsion layers, including a light sensitive silver halide front layer which transmits blue, green, and red light and'is predominantly sensitive to one of these primary colors, a second silver halide layer which is colored by a dyestuii' which is not removable by ordinary photographic treating solutions but which is selectively removable under the iniluence of the photographic image, the dyestu!! absorbing the light of the primary color for-which the front layer is predominantly sensitive but transmitting the light oi' the two other primary colors, the layer being predominantly sensitized to one of these two colors and a third silver halide layer which is transmittant for and predominantly sensitized to the remaining primary color but eiiectively insensitive to light for which the second layer is sensitized, the light transmission characteristic of said material being such that all of said layers can be exposed from the front of said material to light for which they are predominantly sensitive.

f l5. The method oi producing a subtractive multi-color picture from a multi-layer light sensitive silver halide material, having on a common support a colorless surface layer of silver halide emulsion and a direrentiy sensitized silver halide i60 layer which is uniformly pre-dyed by a reducible dyestud resistant to the ordinary photographic treating solutions but capable of being locally destroyed l'under the control of a metallic silver imagel which comprises exposing each of said layers to light to form latent images in the silver halide layers, developing the latent images to iorm silver images, coloring the colorless surface layer uniformly with a reducible dyestui! which transmits blue light and thereafter destroying the dyestuiI in the surface layer and the pre-dyed layer at the points of metallic silver.

Bm GASPAR. 

